US9708491B2 - Optical fiber coating and composition - Google Patents
Optical fiber coating and composition Download PDFInfo
- Publication number
- US9708491B2 US9708491B2 US14/711,909 US201514711909A US9708491B2 US 9708491 B2 US9708491 B2 US 9708491B2 US 201514711909 A US201514711909 A US 201514711909A US 9708491 B2 US9708491 B2 US 9708491B2
- Authority
- US
- United States
- Prior art keywords
- coating composition
- polyol
- group
- derivative compound
- acrylate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 0 C.C.[1*]O[2*]OC(=O)C([3*])=C Chemical compound C.C.[1*]O[2*]OC(=O)C([3*])=C 0.000 description 22
- HPICNEUTLHSETE-UHFFFAOYSA-N C.C.C.C.C.C.[H]N(C(=O)OCCOC1=CC=C(CCCCCCCCC)C=C1)C1CCC(CC2CCC(N([H])C(=O)OCCOC3=CC=C(CCCCCCCCC)C=C3)CC2)CC1 Chemical compound C.C.C.C.C.C.[H]N(C(=O)OCCOC1=CC=C(CCCCCCCCC)C=C1)C1CCC(CC2CCC(N([H])C(=O)OCCOC3=CC=C(CCCCCCCCC)C=C3)CC2)CC1 HPICNEUTLHSETE-UHFFFAOYSA-N 0.000 description 2
- VJJABPKBMFCSPF-UHFFFAOYSA-N C.C.CCCCCCCCCC1=CC=C(OCCO)C=C1 Chemical compound C.C.CCCCCCCCCC1=CC=C(OCCO)C=C1 VJJABPKBMFCSPF-UHFFFAOYSA-N 0.000 description 2
- AYDPXIYHDVNJLM-UHFFFAOYSA-N C.C.[H]C(=C)C(=O)OCCOC1=CC=C(CCCCCCCCC)C=C1 Chemical compound C.C.[H]C(=C)C(=O)OCCOC1=CC=C(CCCCCCCCC)C=C1 AYDPXIYHDVNJLM-UHFFFAOYSA-N 0.000 description 2
- LGMRBFZSICAPPF-UHFFFAOYSA-N C.C.C.C.C.C.C.C.C.CCCCCCCCCC1=CC=C(OCCO)C=C1.O=C=NC1CCC(CC2CCC(N=C=O)CC2)CC1.[H]N(C(=O)OCCOC1=CC=C(CCCCCCCCC)C=C1)C1CCC(CC2CCC(N=C=O)CC2)CC1 Chemical compound C.C.C.C.C.C.C.C.C.CCCCCCCCCC1=CC=C(OCCO)C=C1.O=C=NC1CCC(CC2CCC(N=C=O)CC2)CC1.[H]N(C(=O)OCCOC1=CC=C(CCCCCCCCC)C=C1)C1CCC(CC2CCC(N=C=O)CC2)CC1 LGMRBFZSICAPPF-UHFFFAOYSA-N 0.000 description 1
- VLORHDGNNNWXNU-UHFFFAOYSA-N C.C.C.C.C.C.C.C.[H]N(C(=O)OCCOC(=O)C=C)C1CCC(CC2CCC(N([H])C(=O)OCC(C)OC(=O)N([H])C3CCC(CC4CCC(N([H])C(=O)OCOC(=O)C=C)CC4)CC3)CC2)CC1 Chemical compound C.C.C.C.C.C.C.C.[H]N(C(=O)OCCOC(=O)C=C)C1CCC(CC2CCC(N([H])C(=O)OCC(C)OC(=O)N([H])C3CCC(CC4CCC(N([H])C(=O)OCOC(=O)C=C)CC4)CC3)CC2)CC1 VLORHDGNNNWXNU-UHFFFAOYSA-N 0.000 description 1
- WECSONGGHOKKAW-UHFFFAOYSA-N C.C.C.C.C.C.C=CC(=O)OCOC(=O)COC(=O)CO Chemical compound C.C.C.C.C.C.C=CC(=O)OCOC(=O)COC(=O)CO WECSONGGHOKKAW-UHFFFAOYSA-N 0.000 description 1
- XJLBCSJHFROMTB-UHFFFAOYSA-N C.C.C.C.[H]N(C(=O)OCCOC1=CC=C(CCCCCCCCC)C=C1)C1CCC(CC2CCC(N=C=O)CC2)CC1 Chemical compound C.C.C.C.[H]N(C(=O)OCCOC1=CC=C(CCCCCCCCC)C=C1)C1CCC(CC2CCC(N=C=O)CC2)CC1 XJLBCSJHFROMTB-UHFFFAOYSA-N 0.000 description 1
- UBVLRNJIXRFXND-UHFFFAOYSA-N C.C.C=C=NC1CCC(CC2CCC(N=C=O)CC2)CC1 Chemical compound C.C.C=C=NC1CCC(CC2CCC(N=C=O)CC2)CC1 UBVLRNJIXRFXND-UHFFFAOYSA-N 0.000 description 1
- WSCAESVBMWFTMA-UHFFFAOYSA-N C.C.CC1CCC(CC2CCC(C)CC2)CC1 Chemical compound C.C.CC1CCC(CC2CCC(C)CC2)CC1 WSCAESVBMWFTMA-UHFFFAOYSA-N 0.000 description 1
- WQMUSZZCCRHIHM-UHFFFAOYSA-N C.C.O=C=NC1CCC(CC2CCC(N=C=O)CC2)CC1 Chemical compound C.C.O=C=NC1CCC(CC2CCC(N=C=O)CC2)CC1 WQMUSZZCCRHIHM-UHFFFAOYSA-N 0.000 description 1
- VCTBABBLTFPALD-UHFFFAOYSA-N CCCCCCCCCC1=CC=C(C)C=C1 Chemical compound CCCCCCCCCC1=CC=C(C)C=C1 VCTBABBLTFPALD-UHFFFAOYSA-N 0.000 description 1
- JOBBTVPTPXRUBP-UHFFFAOYSA-N O=C(CCS)OCC(COC(=O)CCS)(COC(=O)CCS)COC(=O)CCS Chemical compound O=C(CCS)OCC(COC(=O)CCS)(COC(=O)CCS)COC(=O)CCS JOBBTVPTPXRUBP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/10—Homopolymers or copolymers of methacrylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/10—Homopolymers or copolymers of methacrylic acid esters
- C09D133/12—Homopolymers or copolymers of methyl methacrylate
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
- C08F220/285—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety
- C08F220/286—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety and containing polyethylene oxide in the alcohol moiety, e.g. methoxy polyethylene glycol (meth)acrylate
-
- C08F2220/286—
Definitions
- This description pertains to coatings and coating compositions for optical fibers. More particularly, this description pertains to alkoxylated acrylate monomers as components of coating compositions for optical fibers. Most particularly, this description pertains to alkoxylated acrylate monomers formed from polyol starting materials, where residual unreacted polyol starting materials in the monomers has been treated to derivatize hydroxyl or alcohol groups.
- the light transmitting performance of an optical fiber is highly dependent upon the properties of the polymer coating that is applied to the fiber during manufacturing.
- a dual-layer coating system is used where a soft inner-primary coating is in contact with the glass fiber and a harder, outer-primary or secondary coating surrounds the inner-primary coating.
- the hard coating allows the fiber to be handled and further processed, while the soft coating plays a key role in dissipating external forces and preventing them from being transferred to the fiber where they can cause microbend induced light attenuation.
- the functional requirements of the inner-primary coating place various requirements on the materials that are used for these coatings.
- the Young's modulus of the inner-primary coating is generally less than 1 MPa, or less than 0.5 MPa.
- the glass transition temperature of the inner-primary coating is less than 5° C., and is ideally about ⁇ 20° C. or less to ensure that the coating remains soft when the fiber is subjected to low temperatures. In order to ensure uniform deposition on the fiber, the coating is applied to the fiber in liquid form and must quickly form a solid having sufficient integrity to support application of the outer-primary coating.
- the tensile strength of the coating which generally decreases as the modulus decreases, must be high enough to prevent tearing defects during draw processing or subsequent processing of the coated fiber during cabling, etc.
- the functional requirements for the outer-secondary coating include properties that provide mechanical rigidity.
- the Young's modulus of the outer-secondary coating is generally greater than 1200 MPa, or greater than 1400 MPa.
- the glass transition temperature of the outer-secondary coating is preferably greater than 30° C., or greater than 40° C., or greater than 50° C.
- optical fiber coatings have traditionally been formulated as mixtures of radiation-curable urethane acrylate oligomers and radiation-curable acrylate functional diluent monomers.
- the acrylate groups Upon exposure to light and in the presence of a photoinitiator, the acrylate groups rapidly polymerize to form a crosslinked polymer network which is further strengthened by the hydrogen bonding interactions between urethane groups along the oligomer backbone.
- Diluent monomers generally have lower molecular weights than the oligomer components of coating compositions and are included in part to facilitate processing by controlling the viscosity of the coating composition. Diluent monomers are also typically reactive and participate in the curing reaction that produces the ultimate coating for the fiber. Diluent monomers are often monofunctional acrylate monomers.
- a common class of diluent monomers is the alkoxylated alkyl acrylates, which can be prepared by a reaction of a polyol and an alkyl-substituted methacrylic acid. Under typical conditions, the reaction to form alkoxylated alkyl acrylates is incomplete and the alkoxylated alkyl acrylate product includes residual amounts of unreacted starting materials.
- alkoxylated alkyl acrylate monomers are often used in an unpurified form and coating compositions based on alkoxylated alkyl acrylate monomers may include residual unreacted starting materials used in the synthesis of alkoxylated alkyl acrylate monomers.
- Ethoxylated nonylphenol and other alkoxylated alcohols may be referred to herein as polyols.
- the European Union for example, has recently identified ethoxylated nonylphenol as a substance of concern.
- Ethoxylated nonylphenol is a staring material for ethoxylated nonylphenol acrylates, which are widely used as diluent monomers in fiber coatings.
- Standard commercial ethoxylated nonylphenol acrylate monomers typically include 1 wt % or more of unreacted ethoxylated nonylphenol.
- the residual amounts of unreacted ethoxylated nonylphenol are present in fiber coatings formed from ethoxylated nonylphenol acrylate monomers and are susceptible to leaching from the fiber coating. When leached, ethoxylated nonylphenol can decompose to form nonylphenol.
- nonylphenol is a regulated substance because it is known to be hazardous to marine life. Current European Union regulations specify a maximum level of 0.1 wt % of ethoxylated nonylphenol.
- compositions that include alkoxylated alkyl acrylate monomers it would be desirable to develop coating compositions based on alkoxylated alkyl acrylate monomers that contain reduced levels of unreacted ethoxylated nonylphenol.
- the present description provides a treated monomer for use in coating compositions and coatings for optical fibers.
- the coating compositions may be used to form primary coatings, secondary coatings, or coatings for fiber ribbons.
- the coating compositions may include one or more monomers, one or more oligomers, a curing agent, and one or more optional additives.
- alkoxylated alkyl acrylate monomers are normally prepared by acrylation reaction of polyol and that conventional sources of alkoxylated alkyl acrylate monomers frequently contain residual amounts of polyol starting material. When cured to form coatings, the residual polyol may become incorporated in the coating and is subject to later release from the coating. Released polyol may subsequently decompose to the corresponding non-alkoxylated alcohol, which may pose a threat to the environment.
- the objective of the present description is to prevent or minimize the potential for release of environmentally harmful components (or precursors thereof) from fiber coatings.
- the strategy disclosed herein provides a derivatization scheme that converts residual polyol components in alkoxylated alkyl acrylate monomers to derivative forms that are environmentally benign and/or less likely to be released from fiber coatings.
- the alkoxylated alkyl acrylate monomer is treated with a derivatizing agent that reacts with the terminal alcohol group to provide a derivative compound.
- the terminal alcohol is functionalized to a different group. The derivative compound thus lacks the terminal alcohol group and is less likely to degrade or otherwise revert back to the corresponding non-alkoxylated alcohol or other lower alkoxylated alcohol.
- the derivatizing agent includes an isocyanate group and the derivatization scheme involves a reaction of the terminal hydroxyl group of residual polyol with the isocyanate group to form a urethane linkage.
- the derivatizing agent may include one or more isocyanate groups.
- the derivatizing agent is a diisocyanate compound and each isocyanate group of the diisocyanate compound reacts with an equivalent of polyol.
- the derivatization reaction may be performed at various stages of the coating formulation process.
- Treatment with the derivatizing agent preferably occurs before curing of the coating composition.
- Treatment of an alkoxylated alkyl acrylate monomer with a derivatizing agent may occur with the alkoxylated alkyl acrylate monomer alone or in combination with one or more other components of a coating composition.
- an alkoxylated alkyl acrylate monomer is treated with a derivatizing agent to derivatize residual polyol before the monomer is combined with other components to form a coating composition.
- an untreated alkoxylated alkyl acrylate monomer is combined with an oligomer and the combination is treated with a derivatizing agent before adding other components of the coating composition.
- an untreated alkoxylated alkyl acrylate monomer is combined with all other components of the coating composition and the coating composition is subsequently treated with a derivatizing agent.
- an alkoxylated alkyl acrylate monomer is treated before incorporation into a coating composition with an amount of derivatizing agent sufficient to reduce the concentration of residual polyol in the alkoxylated acrylate monomer to less than 1.0 wt %, or less than 0.5 wt %, or less than 0.25 wt %, or less than 0.15 wt %, or less than 0.10 wt %, or less than 0.05 wt %.
- the treated alkoxylated alkyl acrylate monomer may then be combined with other components to form a coating composition.
- an alkoxylated alkyl acrylate monomer is treated before incorporation into a coating composition with an amount of derivatizing agent sufficient to reduce the concentration of residual polyol in the coating composition, made by combining alkoxylated alkyl acrylate monomer with other coating components, to less than 1.0 wt %, or less than 0.5 wt %, or less than 0.25 wt %, or less than 0.15 wt %, or less than 0.10 wt %, or less than 0.05 wt %.
- an untreated alkoxylated alkyl acrylate monomer is combined with one or more other components of a coating composition and the mixture is treated with an amount of derivatizing agent sufficient to reduce the concentration of residual polyol in the mixture to less than 1.0 wt %, or less than 0.5 wt %, or less than 0.25 wt %, or less than 0.15 wt %, or less than 0.10 wt %, or less than 0.05 wt %.
- an oligomer with a polyol block is treated before incorporation into a coating composition with an amount of derivatizing agent sufficient to reduce the concentration of residual polyol to less than 1.0 wt %, or less than 0.5 wt %, or less than 0.25 wt %, or less than 0.15 wt %, or less than 0.10 wt %, or less than 0.05 wt %.
- the treated alkoxylated alkyl acrylate monomer may then be combined with other components to form a coating composition.
- the coating composition containing treated alkoxylated alkyl acrylate monomer may be cured to form a coating or other cured product.
- the resulting coating or cured product may have a concentration of residual polyol less than 1.0 wt %, or less than 0.5 wt %, or less than 0.25 wt %, or less than 0.15 wt %, or less than 0.10 wt %, or less than 0.05 wt %.
- the coating composition may include an oligomer with a polyol block.
- Oligomers with a polyol block may be prepared from polyols and may include residual amounts of unreacted polyol. The unreacted polyol may become incorporated in coatings formed by curing coating compositions containing an oligomer with a polyol block.
- Oligomers with residual polyol content may be treated with a derivatizing agent to convert residual polyol to a derivative form lacking a terminal hydroxyl group.
- the derivative form of the polyol may be less susceptible to degradation to the corresponding non-alkoxylated alcohol or other lower alkoxylated alcohol.
- a method of forming a coating comprising:
- FIG. 1 depicts the time evolution of the FTIR spectrum in the region of an isocyanate absorption band for an ethoxylated(4)nonylphenol acrylate monomer during treatment with a diisocyanate derivatizing agent.
- FIG. 2 illustrates the HPLC elution peak of ethoxylated(4)nonylphenol before and after treatment with a diisocyanate derivatizing agent.
- the present description provides a treated monomer for use in coating compositions and coatings for optical fibers.
- the treated monomer includes an alkoxylated alkyl acrylate monomer and a derivative of the corresponding alkoxylated alkyl starting material from which the alkoxylated alkyl acrylate monomer may be derived.
- the alkoxylated alkyl starting material is the non-acrylated hydroxyl containing analog of the alkoxylated alkyl acrylate monomer.
- the alkoxylated alkyl starting material may be referred to herein as a polyol or unreacted polyol starting material.
- the derivative of the polyol is formed by functionalizing the polyol through reaction of the terminal alcohol group of the polyol.
- the treated monomer may be included as a component of a coating composition that may include other monomers, oligomers, and additives as described in greater detail hereinbelow.
- the treated monomer may also be used as a starting material for synthesis of the oligomer component of the coating composition.
- Alkoxylated alkyl acrylate monomers are a common class of diluent monomers used in compositions for coatings for fibers and other applications.
- the alkoxylated alkyl acrylates have the general formula (I):
- R 2 is an alkylene group
- R 1 is hydrogen, an alkyl group, an aromatic group, or an alkyl-substituted aromatic group
- R 3 is hydrogen or an alkyl group.
- R 2 may be a C 1 or higher alkylene group, or a C 2 or higher alkylene group, or a C 3 or higher alkylene group, or a C 4 or higher alkylene group.
- R 2 may be a linear or branched alkylene group.
- Embodiments for R 2 include: methylene (CH 2 ), ethylene ((CH 2 ) 2 ), n-propylene ((CH 2 ) 3 ), or more generally (CH 2 ) n , where n is an integer.
- R 2 include isopropylene and isobutylene.
- R 1 and R 3 are alkyl groups, they may be linear or branched.
- R 1 may be a C 1 or higher alkyl group, or a C 2 or higher alkyl group, or a C 3 or higher alkyl group, or a C 4 or higher alkyl group.
- R 1 may include an aromatic group such as phenyl, phenylene, or alkyl-substituted phenyl.
- the integer n may be in the range from 1-12, or from 1-10, or from 1-8, or from 1-6, or from 1-4, or from 2-9, or from 3-8, or from 4-6. The ranges listed for the integer n are inclusive of the end points.
- the alkoxylated alkyl acrylates can be prepared by a reaction of a polyol having the general formula (II) and (meth)acrylic acid or an alkyl-substituted (meth)acrylic acid having the general formula (III):
- polyol of formula (II) and methacrylic or alkyl-substituted methacrylic acid of formula (III) may be referred to herein as starting materials for preparation of the alkoxylated alkyl acrylate monomer of formula (I).
- Polyol (II) may be referred to herein as the polyol, hydroxyl containing compound, polyol starting material, alkoxylated alkyl or alkoxylated alkyl starting material corresponding to alkoxylated alkyl acrylate (I).
- alkoxylated alkyl acrylate monomer (I) is incomplete and the product may include an unreacted portion of polyol (II) in addition to alkoxylated alkyl acrylate monomer (I).
- coating compositions formulated with alkoxylated alkyl acrylate monomer (I) will include some amount of polyol (II) and the coating formed by curing the coating composition may also include a residual level of polyol (II).
- polyol (II) is susceptible to leaching or otherwise separating from the coating and may enter the surrounding environment where it may degrade to form the corresponding non-alkoxylated alcohol having the formula R 1 OH.
- the corresponding non-alkoxylated alcohol having the formula R 1 OH may also be present in residual amounts or as an unreacted component of polyol (II).
- Synthesis of polyol (II) may entail an alkoxylation reaction of alcohol R 1 OH, where the alkoxylation reaction may not proceed to completion and unless purified or otherwise treated, polyol (II) may include a certain amount of unreacted alcohol R 1 OH.
- polyol (II) is used to form alkoxylated alkyl acrylate (I)
- residual alcohol R 1 OH may become incorporated in coating compositions and coatings formed from alkoxylated alkyl acrylate (I) and may be susceptible to release to the environment.
- the present description provides an alternative strategy for preventing formation of undesirable byproducts from components leached or otherwise released by coating materials.
- the strategy recognizes the likely presence of small amounts of unreacted polyol (II) and/or corresponding non-alkoxylated alcohol R 1 OH in alkoxylated alkyl acrylate monomer (III) and seeks to neutralize the potential environmental impact of unreacted polyol (II) and unreacted corresponding alcohol R 1 OH by converting them to less problematic derivative forms before curing of the coating composition.
- the derivative form is less problematic if released from the coating after curing because it poses a lower threat to the environment and/or is more resistant to degradation to harmful compounds than unreacted polyol (II).
- the derivative form may be less likely to degrade to the non-alkoxylated alcohol R 1 OH corresponding to unreacted polyol (II).
- the derivative form is less problematic because it associates more strongly with the cured coating and is less prone to being leached or otherwise released from the coating after curing.
- Treatment may include reaction of the terminal alcohol of polyol (II) with a derivatizing agent to form a derivative compound having the formula (IV): R 1 O—R 2 n O—R 4 (IV) where R 4 is the residue of the derivatizing agent.
- the terminal alcohol is converted to a non-alcohol group so that R 4 is different from hydrogen.
- Corresponding alcohol R 1 OH may be treated in a similar fashion.
- the derivatizing agent is an acid chloride or a carboxylic acid and reaction of the derivatizing agent with the terminal alcohol group of polyol (II) forms a derivative compound with an ester linkage.
- the derivatizing agent is an isocyanate or a diisocyanate and reaction of the derivatizing agent with the terminal alcohol group of polyol (II) forms a derivative compound with a urethane linkage.
- the derivatization reaction may include a derivatizing agent with multiple functional groups (e.g. a diacid chloride, dicarboxylic acid, diisocyanate, or mixed functional groups such as a derivatizing agent with an isocyanate group and a carboxylic acid group).
- the terminal alcohol group of polyol (II) may be converted to a derivative compound having a different terminal (or interior) functional group and may be further reacted.
- reaction of an isocyanate with polyol (II) produces a derivative compound with a urethane linkage according to the reaction:
- R 5 is an organic group that may optionally include one or more additional functional groups.
- R 6 is an organic group.
- the free isocyanate group may further react with additional equivalents of polyol (II) to produce a derivative compound with two urethane linkages:
- the relative amounts of derivative compounds with one urethane linkage and two urethane linkages can be controlled through the stoichiometric ratio of the diisocyanate to polyol.
- the amount of derivatizing agent can be controlled so that essentially all isocyanate groups react to convert polyol (II) to a derivative form and essentially no unreacted isocyanate groups remain in the monomer composition or coating composition in which the monomer is included.
- the alkoxylated alkyl acrylate monomer is ethoxylated nonylphenol acrylate, which has the formula:
- nonyl group (C 9 H 19 ) may be linear or branched and n ⁇ 1.
- Ethoxylated nonylphenol acrylate may be prepared from the corresponding polyol ethoxylated nonylphenol:
- Ethoxylated nonylphenol may degrade to the corresponding non-ethoxylated alcohol nonylphenol:
- degradation of ethoxylated nonylphenol to nonylphenol can be mitigated by converting ethoxylated nonylphenol to a derivative form that is either less likely to degrade to nonylphenol or less likely to be released from a coating to the environment in the event that residual amounts of it become incorporated in a coating.
- ethoxylated nonylphenol can be converted to a derivative form through reaction with an isocyanate or diisocyanate.
- the derivatizing agent is the diisocyanate H12MDI (4,4′-methylenebis(cyclohexyl isocyanate), which has the formula:
- reaction produces a derivative compound that includes a urethane linkage and a free isocyanate group:
- the free isocyanate group may further react with additional equivalents of ethoxylated nonylphenol to form a derivative compound with two urethane linkages:
- Conversion of polyol (II) to a derivative compound having a urethane linkage is advantageous because the urethane linkage includes a hydrogen donor atom that can participate in hydrogen bonding.
- hydrogen bonding can occur between the urethane group and hydrogen acceptor groups in other components of the coating. The hydrogen bonding strengthens the association of the derivative compound with the cured coating and decreases the likelihood that the derivative compound will leach from or otherwise be released from the coating.
- a urethane linkage in the derivative compound formed from polyol (II) is also advantageous because it is a stable linkage and is unlikely to react or degrade to produce byproducts that may be environmentally hazardous.
- Urethane monomers and oligomers are widely used in fiber coatings because of the stability of the urethane linkage.
- Derivatization of residual polyol (II) with an isocyanate or diisocyanate compound thus produces a derivative compound that is both stable and compatible with other common components present in coating compositions.
- polyol (II) may be present as a residual compound in the oligomer component of the coating composition.
- oligomer acrylates with urethane linkages are frequently used in coating compositions.
- the urethane oligomers are most commonly multifunctional acrylates (e.g. urethane diacrylates or urethane triacrylates) that are included as crosslinking agents in the coating composition.
- Urethane oligomers are commonly prepared from reactions of diols and diisocyanates. Diol reactants include diol variants of polyol (II).
- a representative oligomer formation reaction is:
- oligomers include one or more polyol blocks ((R 7 —O) x ) and one or more isocyanate blocks (C(O)NHR 8 NHC(O)).
- the urethane oligomer product of the reaction can subsequently be acrylated (or diacrylated) by reacting it with methacrylic acid or a substituted methacrylic acid as described hereinabove to form a urethane acrylate oligomer or urethane diacrylate oligomer for use as a component in a fiber coating composition.
- the urethane diacrylate oligomer has the formula:
- the oligomer formation reaction may not proceed to completion and the as-prepared oligomer (acrylated or non-acrylated) may contain some unreacted amount of the diol variant of polyol(II).
- unreacted diol present in the oligomer component of a coating composition may be treated as described hereinabove to provide a derivative compound that is less susceptible to degradation and/or less susceptible to being released from a coating formed from a composition containing an oligomer derived from the diol.
- Fiber coatings are made by curing a coating composition.
- the coating composition typically includes one or more monomers, one or more oligomers, one or more photoinitiators, and one or more additives.
- the monomer(s) and oligomer(s) typically include a radiation curable functional group and the coating is formed by applying the composition to a fiber and curing with a UV lamp.
- the radiation curable functional group may be an acrylate group.
- the monomer(s) may include alkoxylated alkyl acrylate monomers formed from polyol (II).
- Derivatization of unreacted polyol (II) may be accomplished by treating alkoxylated alkyl acrylate monomers with a derivatizing agent. In one embodiment, treatment occurs before combining the alkoxylated alkyl acrylate monomer with other components to form the coating composition. In another embodiment, treatment occurs after combining the alkoxylated alkyl acrylate monomer with other components to form the coating composition and before the coating composition is cured.
- Derivatization of unreacted polyol (II) may be accomplished by treating oligomers and coatings that include blocks derived from polyol (II) with a derivatizing agent. In one embodiment, treatment occurs before combining the oligomer with other components to form the coating composition. In another embodiment, treatment occurs after combining the oligomer with other components to form the coating composition and before the coating composition is cured.
- an alkoxylated alkyl acrylate monomer and an oligomer are treated separately with a derivatizing agent and the derivative forms are combined to form a coating composition.
- an alkoxylated alkyl acrylate monomer is treated with a derivatizing agent and the oligomer is not treated with a derivatizing agent before combining to form a coating composition.
- the coating composition is treated with a derivatizing agent to derivatize the polyol.
- an oligomer treated with a derivatizing agent and an alkoxylated alkyl acrylate monomer is not treated with a derivatizing agent before combining to form a coating composition.
- the coating composition is treated with a derivatizing agent to derivatize the alkoxylated alkyl acrylate monomer.
- a derivatizing agent to derivatize the alkoxylated alkyl acrylate monomer.
- neither an alkoxylated alkyl acrylate monomer nor an oligomer is treated before combining to form a coating composition and both the alkoxylated alkyl acrylate monomer and oligomer are treated with a derivatizing agent after forming the coating composition and before curing the coating composition.
- the amount of derivatizing agent added to an alkoxylated alkyl acrylate monomer or oligomer having a polyol block is preferably enough to minimize the presence of unreacted residual polyol starting material that may be present in an alkoxylated alkyl acrylate monomer, an oligomer with a polyol block, or a coating composition that includes such monomers or oligomers.
- an alkoxylated alkyl acrylate monomer is treated before incorporation into a coating composition with an amount of derivatizing agent sufficient to reduce the concentration of residual polyol to less than 1.0 wt %, or less than 0.5 wt %, or less than 0.25 wt %, or less than 0.15 wt %, or less than 0.10 wt %, or less than 0.05 wt %.
- the derivatizing agent may alternatively be added to the alkoxylated alkyl acrylate monomer in an amount that reacts with substantially all residual polyol.
- the treated alkoxylated alkyl acrylate monomer may then be combined with other components to form a coating composition.
- an oligomer with a polyol block is treated before incorporation into a coating composition with an amount of derivatizing agent sufficient to reduce the concentration of residual polyol to less than 1.0 wt %, or less than 0.5 wt %, or less than 0.25 wt %, or less than 0.15 wt %, or less than 0.10 wt %, or less than 0.05 wt %.
- the derivatizing agent may alternatively be added to the oligomer in an amount that reacts with substantially all residual polyol.
- the treated oligomer may then be combined with other components to form a coating composition.
- an alkoxylated alkyl acrylate monomer is treated before incorporation into a coating composition with an amount of derivatizing agent sufficient to reduce the concentration of residual polyol to less than 1.0 wt %, or less than 0.5 wt %, or less than 0.25 wt %, or less than 0.15 wt %, or less than 0.10 wt %, or less than 0.05 wt %.
- the derivatizing agent may alternatively be added to the alkoxylated alkyl acrylate monomer in an amount that reacts with substantially all residual polyol.
- the treated alkoxylated alkyl acrylate monomer is then combined with an oligomer that has not been treated with a derivatizing agent and with other components to form a coating composition.
- the resulting coating composition is then treated with an amount of derivatizing agent sufficient to reduce the concentration of residual polyol in the coating composition to less than 1.0 wt %, or less than 0.5 wt %, or less than 0.25 wt %, or less than 0.15 wt %, or less than 0.10 wt %, or less than 0.05 wt %.
- the derivatizing agent may alternatively be added to the resulting coating composition in an amount that reacts with substantially all residual polyol.
- an oligomer with a polyol block is treated before incorporation into a coating composition with an amount of derivatizing agent sufficient to reduce the concentration of residual polyol to less than 1.0 wt %, or less than 0.5 wt %, or less than 0.25 wt %, or less than 0.15 wt %, or less than 0.10 wt %, or less than 0.05 wt %.
- the derivatizing agent may alternatively be added to the oligomer in an amount that reacts with substantially all residual polyol.
- the treated oligomer with polyol block is then combined with an alkoxylated alkyl acrylate monomer that has not been treated with a derivatizing agent and with other components to form a coating composition.
- the resulting coating composition is then treated with an amount of derivatizing agent sufficient to reduce the concentration of residual polyol in the coating composition to less than 1.0 wt %, or less than 0.5 wt %, or less than 0.25 wt %, or less than 0.15 wt %, or less than 0.10 wt %, or less than 0.05 wt %.
- the derivatizing agent may alternatively be added to the resulting coating composition in an amount that reacts with substantially all residual polyol.
- an untreated alkoxylated alkyl acrylate monomer and an untreated oligomer with polyol block are combined with other components to form a coating composition and the resulting coating composition is treated before with an amount of derivatizing agent sufficient to reduce the concentration of residual polyol in the coating composition to less than 1.0 wt %, or less than 0.5 wt %, or less than 0.25 wt %, or less than 0.15 wt %, or less than 0.10 wt %, or less than 0.05 wt %.
- the derivatizing agent may alternatively be added to the resulting coating composition in an amount that reacts with substantially all residual polyol.
- the coating composition formed according to any of the foregoing embodiments may be cured to form a coating or other cured product.
- the resulting coating or cured product may have a concentration of residual polyol less than 1.0 wt %, or less than 0.5 wt %, or less than 0.25 wt %, or less than 0.15 wt %, or less than 0.10 wt %, or less than 0.05 wt %.
- the resulting coating or cured product may be essentially free of residual polyol.
- the components of the coating composition include base components and additives.
- the concentration of base components will be expressed in terms of wt % and the concentration of additives will be expressed in terms of pph.
- the weight percent of a particular base component refers to the amount of the component present in the coating composition on a basis that excludes additives.
- the additive-free coating composition includes only base components and may be referred to herein as a base composition or base coating composition.
- Base components include monomer(s), oligomer(s), and curing agent(s). At least one of the monomer(s) or one of the oligomer(s) is curable.
- the base composition minimally includes a curable component (at least one curable monomer or oligomer) and at least one curing agent.
- the curing agent is a polymerization initiator that promotes curing of the curable component.
- the mechanism of curing may be thermal curing or radiation curing.
- the curable component includes a radiation-curable group
- the mechanism of curing is radiation curing and the curing agent is a photoinitiator.
- radiation curing may be accomplished with UV radiation.
- the base composition may include one or more radiation-curable cross-linker oligomers, one or more radiation-curable diluent monomers, one or more non-radiation-curable monomers or oligomers, and one or more curing agents.
- the collective amount of base components in a coating composition is regarded herein as equaling 100 weight percent.
- Additives are optional and may include one or more of an adhesion promoter, an antioxidant, a catalyst, a carrier or surfactant, a tackifier, a stabilizer, and an optical brightener. Representative additives are described in more detail hereinbelow.
- the amount of additives introduced into the coating composition is expressed herein in parts per hundred (pph) relative to the base composition. For example, if 1 g of a particular additive is added to 100 g of base composition, the concentration of additive will be expressed herein as 1 pph.
- the coating composition includes a radiation-curable component and a photoinitiator.
- the radiation-curable component may include one or more radiation-curable compounds.
- Each radiation-curable compound includes a radiation-curable functional group.
- the radiation-curable group may be an ethylenically unsaturated group, such as an acrylate or methacrylate group.
- the radiation-curable compounds may include one or more radiation-curable monomers, one or more radiation-curable oligomers, or a combination of one or more radiation-curable monomers and one or more radiation-curable oligomers.
- the one or more radiation-curable monomers may include one or more monomers having the structure of polyol (II) as modified by incorporation of a radiation-curable functional group, or one or more monomers derived having the structure of polyol (II) as modified by incorporation of a radiation-curable functional group in combination with one or monomers not having the structure of polyol (II) as modified by incorporation of a radiation-curable functional group.
- the one or more radiation-curable oligomers may include one or more oligomers with one or more polyol blocks.
- the one or more radiation-curable oligomers may include one or more oligomers with one or more polyol blocks in combination with one or more oligomers that lack polyol blocks.
- the radiation-curable monomer(s) or oligomer(s) may be monofunctional or multifunctional.
- Multifunctional radiation-curable compounds have two or more radiation-curable functional groups and may function as crosslinking agents.
- Multifunctional radiation-curable monomer(s) or oligomer(s) may be referred to herein as “crosslinkers”.
- Radiation-curable monomer(s) may function as reactive diluent(s) in the coating composition and may afford control over the viscosity of the coating composition to facilitate processing.
- the radiation-curable monomer(s) have a molecular weight in the range from 120-600 g/mol.
- the radiation-curable component may include a radiation-curable monofunctional or multifunctional monomer.
- the monomer may include a monofunctional or multifunctional (meth)acrylate monomer.
- (meth)acrylate means acrylate or methacrylate.
- the monomer may include polyether (meth)acrylates, polyester (meth)acrylates, or polyol (meth)acrylates.
- the multifunctional monomer may be a di(meth)acrylate, tri(meth)acrylate, tetra(meth)acrylate, or higher (meth)acrylate.
- Monofunctional or multifunctional polyol (meth)acrylates may include monofunctional or multifunctional polyalkoxy(meth)acrylates (e.g.
- the monofunctional or multifunctional monomer may lack urethane groups, urea groups, isocyanate groups, and hydrogen-donor groups. Lack of hydrogen-donor groups precludes the monofunctional or multifunctional monomer from functioning as a hydrogen donor in hydrogen bonding interactions.
- Radiation-curable monomers may also include ethylenically-unsaturated compounds, ethoxylated (meth)acrylates, alkoxylated (meth)acrylates, ethoxylated alkylphenol mono(meth)acrylates, propylene oxide (meth)acrylates, n-propylene oxide (meth)acrylates, isopropylene oxide (meth)acrylates, monofunctional (meth)acrylates, monofunctional aliphatic epoxy (meth)acrylates, multifunctional (meth)acrylates, multifunctional aliphatic epoxy (meth)acrylates, and combinations thereof.
- the radiation-curable monomer may include compounds having the general formula R′′—R′—O—(CH 2 CH(CH 3 )—O) n —COCH ⁇ CH 2 , where R′ and R′′ are aliphatic, aromatic, or a mixture of both, and n is in the range from 1 to 10 (inclusive), or R′—O—(CH 2 CH(CH 3 )—O) n —COCH ⁇ CH 2 , where R′ is aliphatic or aromatic, and n is in the range from 1 to 10 (inclusive), or formula R′′—R′—O—(CH 2 CH 2 —O) n —COCH ⁇ CH 2 , where R′ and R′′ are aliphatic, aromatic, or a mixture of both, and n is in the range from 1 to 10 (inclusive), or R′—O—(CH 2 CH 2 —O) n —COCH ⁇ CH 2 , where R′ is aliphatic or aromatic, and n is in the range from 1 to 10 (inclusive).
- the radiation-curable monomer includes one or more polyols that contain one or more ⁇ , ⁇ -unsaturated ester, amide, imide, or vinyl ether groups, or combinations thereof.
- Exemplary classes of polyols include, without limitation, polyol acrylates, polyol methacrylates, polyol maleates, polyol fumarates, polyol acrylamides, polyol maleimides or polyol vinyl ethers comprising one or more acrylate, methacrylate, maleate, fumarate, acrylamide, maleimide or vinyl ether group.
- the polyol moiety of the radiation-curable monomer can be a polyether polyol, a polyester polyol, a polycarbonate polyol, or a hydrocarbon polyol.
- Exemplary monofunctional ethylenically unsaturated radiation-curable monomers include, without limitation, hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate; long- and short-chain alkyl acrylates such as methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, amyl acrylate, isobutyl acrylate, t-butyl acrylate, pentyl acrylate, isoamyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, isooctyl acrylate (e.g.
- SR440 available from Sartomer Company, Inc. and Ageflex FA8 available from CPS Chemical Co.
- undecyl acrylate, dodecyl acrylate, tridecyl acrylate e.g. SR489 available from Sartomer Company, Inc.
- lauryl acrylate e.g. SR335 available from Sartomer Company, Inc., Ageflex FA12 available from CPS Chemical Co.
- octadecyl acrylate and stearyl acrylate (e.g. SR257 available from Sartomer Company, Inc.); aminoalkyl acrylates such as dimethylaminoethyl acrylate, diethylaminoethyl acrylate, and 7-amino-3,7-dimethyloctyl acrylate; alkoxyalkyl acrylates such as butoxylethyl acrylate, ethyoxylated lauryl acrylate (e.g.
- CD9075 Sartomer USA (Exton, Pa.), epoxy acrylate (e.g., CN120, Sartomer USA (Exton, Pa.), and EBECRYL 3201 and 3604, Cytec Industries Inc. (Woodland Park, N.J.)), phenoxyethyl acrylate (e.g. SR339 available from Sartomer Company, Inc., Ageflex PEA available from BASF, and Photomer 4035 available from IGM Resins), phenoxyglycidyl acrylate (e.g. CN131 available from Sartomer Company, Inc.), lauryloxyglycidyl acrylate (e.g.
- CN130 available from Sartomer Company, Inc.
- 2-(2-ethoxyethoxyl)ethyl acrylate e.g. SR256 available from Sartomer Company, Inc.
- single and multi-ring cyclic aromatic or non-aromatic acrylates such as cyclohexyl acrylate, benzyl acrylate, dicyclopentadiene acrylate, dicyclopentanyl acrylate, tricyclodecanyl acrylate, bornyl acrylate, isobornyl acrylate (e.g. SR423 and SR506 available from Sartomer Company, Inc., and Ageflex IBOA available from CPS Chemical Co.), tetrahydrofurfuryl acrylate (e.g.
- SR285 available from Sartomer Company, Inc.
- caprolactone acrylate e.g. SR495 available from Sartomer Company, Inc.; and Tone M100 available from Union Carbide Company, Danbury, Conn.
- acryloylmorpholine alcohol-based acrylates such as polyethylene glycol monoacrylate, polypropylene glycol monoacrylate, methoxyethylene glycol acrylate, methoxypolypropylene glycol acrylate, methoxypolyethylene glycol acrylate, ethoxydiethylene glycol acrylate, and various alkoxylated alkylphenol acrylates such as ethoxylated(4) nonylphenol acrylate (e.g.
- Photomer 4003 available from IGM Resins; and SR504 available from Sartomer Company, Inc.
- propoxylatednonylphenol acrylate e.g. Photomer 4960 available from IGM Resins
- acrylamides such as diacetone acrylamide, isobutoxymethyl acrylamide, N,N′-dimethyl-aminopropyl acrylamide, N,N-dimethyl acrylamide, N,N-diethyl acrylamide, and t-octyl acrylamide
- vinylic compounds such as N-vinylpyrrolidone and N-vinylcaprolactam (both available from International Specialty Products, Wayne, N.J.)
- acid esters such as maleic acid ester and fumaric acid ester.
- the radiation-curable component of the coating composition may include multifunctional (meth)acrylate monomer(s).
- Multifunctional (meth)acrylates are (meth)acrylates having two or more curable (meth)acrylate moieties per molecule.
- the multifunctional (meth)acrylate may have three or more curable (meth)acrylate moieties per molecule.
- the multifunctional (meth)acrylate may have four or more curable (meth)acrylate moieties per molecule.
- Suitable multifunctional ethylenically unsaturated monomers include, without limitation, methylolpropane polyacrylates with and without alkoxylation such as ethoxylated trimethylolpropane triacrylate with the degree of ethoxylation being 3 or greater, preferably ranging from 3 to about 30 (e.g. Photomer 4149 available from IGM Resins, and SR 351 and SR499 available from Sartomer Company, Inc.), methylolpropane polyacrylates with and without alkoxylation such as trimethylolpropane triacrylate (e.g., triproplyleneglycol diacrylate (e.g.
- Photomer 4096 available from IGM Resins; and SR9020 available from Sartomer Company, Inc.
- erythritol polyacrylates with and without alkoxylation such as pentaerythritol tetraacrylate (e.g. SR295 available from Sartomer Company, Inc.), ethoxylated pentaerythritol tetraacrylate (e.g. SR494 available from Sartomer Company, Inc.), and dipentaerythritol pentaacrylate (e.g.
- CD564 available from Sartomer Company, Inc.
- tripropylene glycol diacrylate e.g. SR306 available from Sartomer Company, Inc.
- ethoxylated polyethylene glycol diacrylate with a degree of ethoxylation being 2 or greater, preferably ranging from about 2 to 30
- epoxy acrylates formed by adding acrylate to bisphenol A diglycidylether and the like e.g. Photomer 3016 available from IGM Resins
- single and multi-ring cyclic aromatic or non-aromatic polyacrylates such as dicyclopentadiene diacrylate.
- the radiation-curable component of the coating composition may include an N-vinyl amide such as an N-vinyl lactam, or N-vinyl pyrrolidinone, or N-vinyl caprolactam.
- the radiation-curable component may include a radiation-curable monofunctional or multifunctional oligomer.
- the oligomer may be a (meth)acrylate-terminated oligomer.
- the oligomer may include polyether acrylates (e.g., GENOMER 3456, available from Rahn USA (Aurora, Ill.)), polyester acrylates (e.g., EBECRYL 80, 584 and 657, available from Cytec Industries Inc. (Woodland Park, N.J.)), or polyol acrylates.
- the oligomer may be a di(meth)acrylate, tri(meth)acrylate, tetra(meth)acrylate, or higher (meth)acrylate.
- Polyol (meth)acrylates may include polyalkoxy(meth)acrylates or polyol(meth)acrylates. Examples include polyethylene glycol diacrylate and polypropylene glycol diacrylate.
- the monofunctional or multifunctional oligomer may lack urethane groups, urea groups, isocyanate groups, and/or hydrogen-donor groups.
- the radiation-curable oligomer may include one or more polyols that contain two or more ⁇ , ⁇ -unsaturated ester, amide, imide, or vinyl ether groups, or combinations thereof.
- Exemplary classes of these polyol-containing oligomers include, without limitation, polyol acrylates, polyol methacrylates, polyol maleates, polyol fumarates, polyol acrylamides, polyol maleimides or polyol vinyl ethers comprising more than one acrylate, methacrylate, maleate, fumarate, acrylamide, maleimide or vinyl ether group.
- the polyol moiety can be a polyether polyol, a polyester polyol, a polycarbonate polyol, or a hydrocarbon polyol.
- a monofunctional radiation-curable monomer may be present in the radiation-curable coating composition at a concentration from 10-60 wt %, or from 10-30 wt %, or from 30-60 wt %, or from 40-80 wt %, or from 60-80 wt %.
- the radiation-curable coating composition may include one or more monofunctional (meth)acrylate monomers in an amount from 5-95 wt %, or from 0-75 wt %, or from 40-65 wt %.
- the radiation-curable coating composition may include one or more monofunctional aliphatic epoxy (meth)acrylate monomers in an amount from 5-40 wt %, or from 10-30 wt %.
- a multifunctional radiation-curable monomer may be present in the radiation-curable coating composition at a concentration from 0.05-15 wt %, or from 0.1-10 wt %, or from 0.5-10 wt %, or from 1-5 wt %, or from 1-10 wt %, or from 1-20 wt %, or from 1-50 wt %, or from 2-8 wt %, or from 5-40 wt %, or from 10-30 wt %, or from 20-30 wt %.
- the total monomer content of the radiation-curable coating composition may be between about 5 wt % and about 95 wt %, or between about 30 wt % and about 75 wt %, or between about 40 wt % and about 65 wt %.
- the total oligomer content of the radiation-curable coating composition may be less than 5 wt %, or between about 5 wt % and about 95 wt %, or between about 25 wt % and about 65 wt %, or between about 35 wt % and about 55 wt %.
- the oligomer content of secondary coatings is generally higher than the oligomer content of primary coatings.
- the base coating composition further includes one or more curing agents.
- a curing agent is a polymerization initiator that initiates a curing reaction of curable components in the coating composition.
- the polymerization initiator is a reagent that is suitable to cause polymerization (i.e., curing) of the composition after its application to a glass fiber or other receiving surface.
- Polymerization initiators suitable for use in coating compositions include thermal initiators, chemical initiators, electron beam initiators, and photoinitiators. Photoinitiators are the preferred polymerization initiators. For most acrylate-based coating formulations, conventional photoinitiators, such as the known ketonic photoinitiators and/or phosphine oxide photoinitiators, are preferred.
- the photoinitiator When used in the coating compositions, the photoinitiator is present in an amount sufficient to provide rapid curing upon exposure of the coating composition to curing radiation.
- the curing radiation may be UV radiation.
- amount of the one or more photoinitiators in the coating composition is between about 0.5 to about 10.0 percent by weight, more preferably between about 1.5 to about 7.5 percent by weight.
- the photoinitiator when used in a small but effective amount to promote radiation cure, should provide reasonable cure speed without causing premature gelation of the coating composition.
- a desirable cure speed is any speed sufficient to cause substantial curing of the coating materials.
- a cure speed for coating thicknesses of about 25-35 ⁇ m is, e.g., less than 1.0 J/cm 2 , preferably less than 0.5 J/cm 2 .
- Suitable photoinitiators include, without limitation, 1-hydroxycyclohexylphenyl ketone (e.g. Irgacure 184 available from BASF), (2,6-dimethoxybenzoyl)-2,4,4-trimethylpentyl phosphine oxide (e.g. commercial blends Irgacure 1800, 1850, and 1700 available from BASF), 2,2-dimethoxyl-2-phenyl acetophenone (e.g. Irgacure 651, available from BASF), bis(2,4,6-trimethyl benzoyl)phenyl-phosphine oxide (e.g.
- 1-hydroxycyclohexylphenyl ketone e.g. Irgacure 184 available from BASF
- (2,6-dimethoxybenzoyl)-2,4,4-trimethylpentyl phosphine oxide e.g. commercial blends Irgacure 1800, 1850, and 1700 available from BASF
- Irgacure 819 available from BASF
- (2,4,6-trimethylbenzoyl)diphenyl phosphine oxide e.g. Lucerin TPO available from BASF, Kunststoff, Germany
- ethoxy(2,4,6-trimethylbenzoyl)phenyl phosphine oxide e.g. Lucerin TPO-L from BASF
- the coating compositions may also include one or more additives.
- Representative additives include an adhesion promoter, an antioxidant, a catalyst, a carrier or surfactant, a tackifier, a stabilizer, and an optical brightener.
- Some additives e.g., catalysts, reactive surfactants, and optical brighteners
- Other additives may influence the integrity of the cured product of the coating composition (e.g., protect against de-polymerization or oxidative degradation).
- an adhesion promoter enhances the adhesion of the primary coating to the underlying glass fiber.
- Any suitable adhesion promoter can be employed.
- a suitable adhesion promoter include, without limitation, organofunctional silanes, titanates, zirconates, and mixtures thereof.
- One preferred class are the poly(alkoxy)silanes.
- Suitable alternative adhesion promoters include, without limitation, bis(trimethoxysilylethyl)benzene, 3-mercaptopropyltrimethoxysilane (3-MPTMS, available from United Chemical Technologies, Bristol, Pa.; also available from Gelest, Morrisville, Pa.), 3-acryloxypropyltrimethoxysilane (available from Gelest), and 3-methacryloxypropyltrimethoxysilane (available from Gelest), and bis(trimethoxysilylethyl)benzene (available from Gelest).
- Other suitable adhesion promoters are described in U.S. Pat. Nos. 4,921,880 and 5,188,864 to Lee et al., each of which is hereby incorporated by reference.
- the adhesion promoter if present, is used in an amount between about 0.1 to about 10 pph, more preferably about 0.25 to about 3 pph.
- antioxidants include, without limitation, bis hindered phenolic sulfide or thiodiethylene bis(3,5-di-tert-butyl)-4-hydroxyhydrocinnamate (e.g. Irganox 1035, available from BASF).
- the antioxidant if present, is used in an amount between about 0.1 to about 3 pph, more preferably about 0.25 to about 2 pph.
- An exemplary catalyst is a tin-catalyst, which is used to catalyze the formation of urethane bonds in some non-radiation curable components. Whether the catalyst remains as an additive of the non-radiation curable component or additional quantities of the catalyst are introduced into the composition, the presence of the catalyst can act to stabilize the non-radiation curable component(s) in the composition.
- Suitable carriers include polyalkoxypolysiloxanes.
- Exemplary preferred carriers are available from Goldschmidt Chemical Co. (Hopewell, Va.) under the tradename TEGORAD 2200 and TEGORAD 2700 (acrylated siloxane). These reactive surfactants may be present in a preferred amount between about 0.01 to about 5 pph, more preferably about 0.25 to about 3 pph.
- Other classes of suitable carriers include non-reactive surfactants. Examples of suitable non-reactive surfactants include, without limitation, Tegoglide 435 (polyalkoxy-polysiloxane) available from Goldschmidt Chemical Co. The non-reactive surfactants may be present in a preferred amount between about 0.01 pph to about 10 pph, more preferably about 0.05 pph to about 5 pph, most preferably about 0.1 pph to about 2.5 pph.
- Suitable carriers may also be ambiphilic molecules.
- An ambiphilic molecule is a molecule that has both hydrophilic and hydrophobic segments. The hydrophobic segment may alternatively be described as a lipophilic (fat/oil loving) segment.
- a tackifier is an example of one such ambiphilic molecule.
- a tackifier is a molecule that can modify the time-sensitive rheological property of a polymer product. In general a tackifier additive will make a polymer product act stiffer at higher strain rates or shear rates and will make the polymer product softer at low strain rates or shear rates.
- a tackifier is an additive that is commonly used in the adhesives industry, and is known to enhance the ability of a coating to create a bond with an object that the coating is applied upon.
- One preferred tackifier is Uni-Tac® R-40 (hereinafter “R-40”) available from International Paper Co., Purchase, N.Y. R-40 is a tall oil rosin, which contains a polyether segment, and is from the chemical family of abietic esters.
- R-40 Uni-Tac® R-40
- R-40 Uni-Tac® R-40
- R-40 Uni-Tac® R-40
- R-40 Uni-Tac® R-40
- a suitable alternative tackifier is the Escorez® series of hydrocarbon tackifiers available from Exxon.
- the aforementioned carriers may also be used in combination.
- the tackifier is present in the composition in an amount between about 0.01 to about 10 pph, more preferably in the amount between about 0.05 to about 5 pph.
- Any suitable stabilizer can be employed.
- One preferred stabilizer is a tetrafunctional thiol, e.g., pentaerythritol tetrakis(3-mercaptopropionate) from Sigma-Aldrich (St. Louis, Mo.).
- the stabilizer if present, is used in an amount between about 0.01 to about 1 pph, more preferably about 0.01 to about 0.2 pph.
- optical brightener Any suitable optical brightener can be employed.
- exemplary optical brighteners include, without limitation, Uvitex OB, a 2,5-thiophenediylbis(5-tert-butyl-1,3-benzoxazole) (BASF); Blankophor KLA, available from Bayer; bisbenzoxazole compounds; phenylcoumarin compounds; and bis(styryl)biphenyl compounds.
- the optical brightener is desirably present in the composition at a concentration of about 0.003 to about 0.5 pph, more preferably about 0.005 to about 0.3 pph.
- the fiber includes a primary coating and a secondary coating, where the primary coating surrounds the glass region (core+cladding) and the secondary coating surrounds the primary coating.
- the primary coating is a treated coating composition or a coating composition with one or more treated monomer(s) and/or oligomer(s).
- the secondary coating is a treated coating composition or a coating composition with one or more treated monomer(s) and/or oligomer(s).
- the primary coating is a treated coating composition or a coating composition with one or more treated monomer(s) and/or oligomer(s) and the secondary coating is a treated coating composition or a coating composition with one or more treated monomer(s) and/or oligomer(s).
- the fiber coating process involves fabricating the glass fiber (using methods familiar to the skilled artisan), applying a curable primary coating composition to the glass fiber, polymerizing the curable primary coating composition to form the primary coating material, applying a curable secondary coating composition to the cured primary coating, and polymerizing the curable secondary composition to form the secondary coating material.
- a curable primary coating composition to the glass fiber
- polymerizing the curable primary coating composition to form the primary coating material
- applying a curable secondary coating composition to the cured primary coating
- polymerizing the curable secondary composition to form the secondary coating material.
- the curable secondary coating composition can be applied to the coated fiber before polymerizing the curable primary coating composition, in which case both coating compositions may be cured simultaneously. This is known as a “wet-on-wet” process.
- the primary and secondary coating compositions are coated on a glass fiber using conventional processes, for example, on a draw tower.
- glass fibers can be drawn from a specially prepared, cylindrical silica-based preform that has been locally and symmetrically heated to a temperature, e.g., of about 2000° C.
- a glass fiber is drawn from the molten material and cooled.
- One or more coating compositions are applied to the glass fiber after it has been drawn from the preform, preferably immediately after cooling.
- the coating compositions are then cured to produce the coated optical fiber.
- the method of curing can be thermal, chemical, or radiation induced, such as by exposing the applied (and un-cured) coating composition on the glass fiber to ultraviolet light, actinic radiation, microwave radiation, or electron beam, depending upon the nature of the coating composition(s) and curing agent being employed.
- One method of applying dual layers of coating compositions to a moving glass fiber is disclosed in U.S. Pat. No. 4,474,830 to Taylor, which is hereby incorporated by reference in its entirety.
- Another method for applying dual layers of coating compositions onto a glass fiber is disclosed in U.S. Pat. No. 4,581,165 to Rannell et al., which is hereby incorporated by reference in its entirety.
- the present coating compositions may also be cured to form coatings for an optical fiber ribbon.
- An optical fiber ribbon includes a plurality of optical fibers embedded in an encapsulating matrix, where the encapsulating matrix may be a cured coating composition.
- the optical fibers are substantially aligned relative to one another in a substantially planar relationship in forming the ribbon. It is preferable that the optical fibers are not displaced from a common plane by a distance of more than about one-half the diameter of the individual fibers. By “substantially aligned”, it is intended that the optical fibers are generally parallel with other optical fibers along the length of the fiber optic ribbon.
- the optical fibers in fiber optic ribbons may be encapsulated by the matrix in any known configuration (e.g., edge-bonded ribbon, thin-encapsulated ribbon, thick-encapsulated ribbon, or multi-layer ribbon) by conventional methods of making fiber optic ribbons.
- the encapsulating matrix can be the cured product of a coating composition in accordance with the present description.
- the encapsulating matrix has characteristics consistent with a secondary composition to ensure adequate durability and strength.
- the optical fibers in a fiber ribbon may include a dual-layer coating system (for example, the primary and secondary coatings described hereinabove), and may be colored with a marking ink.
- the encapsulating matrix of the fiber ribbon may simultaneously serve as the secondary coating of the fibers.
- a plurality of optical fibers having a primary coating is aligned and the matrix composition is applied and cured.
- the following examples consider fiber coatings formed by curing coating compositions that include ethoxylated nonylphenol acrylate as a component.
- the ethoxylated nonylphenol acrylate is included as a reactive diluent monomer in the coating compositions.
- residual amounts of ethoxylated nonylphenol may be present in the source of ethoxylated nonylphenol acrylate and may become incorporated in coatings formed by curing coating compositions that include ethoxylated nonylphenol acrylate.
- the level of ethoxylated nonylphenol in the coatings of several commercial optical fibers is listed in Table 1. The coatings are proprietary to the manufacturer and are listed without reference to the manufacturer or supplier.
- Ethoxylated Nonyphenol Coating (wt %) A 0.384 B 0.416 C 0.287 D 0.273 E 0.439 F 0.408 G 0.520 H 0.426 I 0.530 J 0.255 K 0.183 The data in the table indicate that ethoxylated nonylphenol is present at residual levels in several widely used fiber coatings. In each of the coatings listed, the concentration of ethoxylated nonylphenol exceeds the 0.1 wt % limit specified by the European Union in its REACh report identifying ethoxylated nonylphenol as a substance of very high concern (SVHC).
- SVHC very high concern
- the HPLC measurements revealed peaks corresponding to three components: ethoxylated(4)nonylphenol acrylate, ethoxylated(4)nonylphenol, and the Michael addition product of ethoxylated(4)nonylphenol acrylate and ethoxylated(4)nonylphenol.
- the peaks were quantified and the relative weight percent of each of the three components was determined.
- the results of the HPLC analysis of the sample are shown in Table 2, where the numbers in the table correspond to the amount of each component in the sample in units of wt % (weight percent):
- tensile properties of films formed from a Control coating composition and a Test coating composition were measured.
- the components and amounts used to prepare the two coating compositions are listed in Table 3.
- the Test composition also included 75 g of the derivatizing agent H12MDI (4,4′-methylenebis(cyclohexyl isocyanate). No derivatizing agent was added to the Control composition.
- BR3741 is an oligomer having the formula:
- SR 504 is a monomer having the formula
- Caprolactone acrylate is a monomer having the formula
- Irgacure 819 is bis(2,4,6-trimethyl benzoyl)phenyl-phosphine oxide) and is a photoinitiator.
- Pentaerythritol tetrakis(3-mercaptopropionate) is a stabilizer and has the formula:
- Irganox 1035 is thiodiethylene bis(3,5-di-tert-butyl)-4-hydroxyhydrocinnamate and is an antioxidant. 3-acryloxypropyltrimethoxysilane is an adhesion promoter.
- the Test composition included the derivatizing agent H12MDI and was prepared by first combining the BR3741 oligomer and the SR504 monomer. 75 g of H12MDI was then added and the mixture was stirred at 70° C. for several hours to insure that the derivatization reaction was complete. Derivatization was intended to derivatize residual ethoxylated(4)nonylphenol present in the SR504 monomer. Derivatization proceeded according to the reaction:
- FIG. 2 shows an HPLC measurement of the peak associated with ethoxylated(4)nonylphenol before introduction of the derivatizing agent and after completion of the derivatization reaction.
- the HPLC peak exhibited high intensity before the derivatization reaction and was essentially eliminated at the conclusion of the derivatization reaction.
- the data in FIGS. 1 and 2 show simultaneous depletion of H12MDI and ethoxylated(4) nonylphenol as expected from the derivatization reaction.
- the relative concentrations (in wt %) of ethoxylated(4)nonylphenol acrylate, ethoxylated(4)nonylphenol, and the Michael addition product of ethoxylated(4)nonylphenol acrylate and ethoxylated(4)nonylphenol of the derivatized mixture of BR3741 oligomer and SR504 monomer were determined from HPLC data and are reported in Table 4. Data for the untreated (non-derivatized) SR504 monomer reported above in Table 2 are repeated for comparison purposes. The data indicate that derivatization of ethoxylated(4)nonylphenol acrylate with H12MDI eliminated residual ethoxylated(4)nonylphenol to a level below the detection limit of the HPLC measurement.
- the remaining components (caprolactone acrylate, Irgacure 819, pentaerythritol tetrakis(3-mercaptopropionate), Irganox 1035, 3-acryloxypropyltrimethoxysilane) of the formulation were added to the derivatized mixture of BR3741 oligomer and SR504 monomer to form the Test coating composition.
- Test coating composition and Control coating composition were cured to form films for measurements of tensile properties and T g .
- the films were prepared by drawing down portions of the formulations on release paper using a 5 mil ( ⁇ 125 ⁇ m) draw down bar. Films were cured using a Fusion D lamp with a nitrogen purge. The films received a dose of approximately 1200 mJ/cm 2 . All film samples were allowed to condition overnight in a controlled environment at 23° C. and 50% relative humidity. The thickness of the cured films was ⁇ 80 ⁇ m.
- Tensile properties of the cured films were measured using a Sintech MTS tensile test instrument according to procedures set forth in ASTM Standard D882-97. Films were cut to a specified length and width (15 cm ⁇ 1.3 cm) and mounted in the test instrument. The gauge length used for testing was 5.1 cm and the test speed was 2.5 cm/minute. Young's modulus, tensile strength, and % elongation values were recorded.
- ranges disclosed herein are inclusive of end points.
- a statement that “n is in the range from 1 to 10”, “n is in the range from 1-10”, or like statement shall be construed to mean that n may be 1, 10, or any integer greater than 1 and less than 10.
- a statement that a particular component is present in a coating composition “in an amount from 20-30 wt %”, or “in an amount between 20-30 wt %”, or “in an amount between 20 and 30 wt %”, or like statement shall be constructed to mean that the wt % of the component may be 20 wt %, 30 wt %, or any wt % between 20 wt % and 30 wt %.
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Paints Or Removers (AREA)
- Polyurethanes Or Polyureas (AREA)
- Surface Treatment Of Glass Fibres Or Filaments (AREA)
- Optical Fibers, Optical Fiber Cores, And Optical Fiber Bundles (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US14/711,909 US9708491B2 (en) | 2014-06-04 | 2015-05-14 | Optical fiber coating and composition |
US15/582,966 US10030164B2 (en) | 2014-06-04 | 2017-05-01 | Optical fiber coating and composition |
US16/042,051 US10377915B2 (en) | 2014-06-04 | 2018-07-23 | Optical fiber coating and composition |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US201462007448P | 2014-06-04 | 2014-06-04 | |
US14/711,909 US9708491B2 (en) | 2014-06-04 | 2015-05-14 | Optical fiber coating and composition |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US15/582,966 Division US10030164B2 (en) | 2014-06-04 | 2017-05-01 | Optical fiber coating and composition |
Publications (2)
Publication Number | Publication Date |
---|---|
US20150353757A1 US20150353757A1 (en) | 2015-12-10 |
US9708491B2 true US9708491B2 (en) | 2017-07-18 |
Family
ID=53499073
Family Applications (3)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US14/711,909 Active US9708491B2 (en) | 2014-06-04 | 2015-05-14 | Optical fiber coating and composition |
US15/582,966 Active US10030164B2 (en) | 2014-06-04 | 2017-05-01 | Optical fiber coating and composition |
US16/042,051 Active US10377915B2 (en) | 2014-06-04 | 2018-07-23 | Optical fiber coating and composition |
Family Applications After (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US15/582,966 Active US10030164B2 (en) | 2014-06-04 | 2017-05-01 | Optical fiber coating and composition |
US16/042,051 Active US10377915B2 (en) | 2014-06-04 | 2018-07-23 | Optical fiber coating and composition |
Country Status (5)
Country | Link |
---|---|
US (3) | US9708491B2 (ja) |
EP (1) | EP3152262B1 (ja) |
JP (2) | JP6803752B2 (ja) |
CN (1) | CN106795389B (ja) |
WO (1) | WO2015187899A1 (ja) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20170233600A1 (en) * | 2014-06-04 | 2017-08-17 | Corning Incorporated | Optical fiber coating and composition |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2017103655A1 (en) * | 2015-12-16 | 2017-06-22 | Prysmian S.P.A. | Optical fibre with enhanced high temperature resistance |
CA3040492A1 (en) * | 2018-04-18 | 2019-10-18 | The University Of Akron | Functionalized polymer compositions for low voc coalescence of water based emulsions |
US11174413B2 (en) | 2018-07-13 | 2021-11-16 | Corning Incorporated | Optical fiber coating compositions with hydrogen bonding, non-covalent bonding, cross-linkers |
JP2022552367A (ja) * | 2019-10-14 | 2022-12-15 | コーニング インコーポレイテッド | ポリマー系部分、接着剤、折畳み可能な装置および製造する方法 |
Citations (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4474830A (en) | 1982-12-29 | 1984-10-02 | At&T Bell Laboratories | Multiple coating of fibers |
US4581165A (en) | 1984-06-14 | 1986-04-08 | Eli Lilly And Company | Anti-diabetic compounds |
US20030044140A1 (en) * | 1999-12-30 | 2003-03-06 | Fewkes Edward J. | Composition containing tackifier and method of modifying time-sensitive rheological properties of optical fiber coating |
US6563996B1 (en) * | 1999-12-30 | 2003-05-13 | Corning Incorporated | Optical fibers prepared with a primary coating composition including a monomer with a pendant hydroxyl functional group |
WO2005017053A1 (en) | 2003-08-13 | 2005-02-24 | Luvantix Co., Ltd. | Photocurable and antistatic resin composition for coating optical fiber |
US20050148738A1 (en) * | 2003-11-25 | 2005-07-07 | Leon Joseph A. | Caprolactone-grafted phenoxy resin oligomer and formulations containing it |
US7010206B1 (en) | 2004-09-08 | 2006-03-07 | Corning Incorporated | Coated optical fiber and optical fiber coating system including a fast-gelling primary coating |
US20080125546A1 (en) * | 2004-09-24 | 2008-05-29 | Hiroshi Yamaguchi | Curable Liquid Resin Optical Fiber Up Jacket Composition |
WO2008076299A1 (en) | 2006-12-14 | 2008-06-26 | Dsm Ip Assets B.V. | D1363 bt radiation curable primary coatings on optical fiber |
WO2010008174A2 (en) * | 2008-07-16 | 2010-01-21 | Sscp Co., Ltd. | Photocurable coating composition which provides a coating layer having improved hot water resistance |
EP2322576A2 (en) | 2008-08-26 | 2011-05-18 | SSCP Co., Ltd. | Photopolymerized resin composition and optical fiber manufactured with same |
US20110217011A1 (en) * | 2010-03-02 | 2011-09-08 | Kevin Wallace Bennett | High numerical aperture multimode optical fiber |
US8093322B2 (en) * | 2005-10-27 | 2012-01-10 | Corning Incorporated | Non-reactive additives for fiber coatings |
US20120196122A1 (en) * | 2009-12-17 | 2012-08-02 | Timothy Bishop | Led curing of radiation curable optical fiber coating compositions |
WO2014081004A1 (ja) | 2012-11-22 | 2014-05-30 | 日本合成化学工業株式会社 | 活性エネルギー線硬化性樹脂組成物、コーティング剤組成物、及び積層体 |
WO2014172143A1 (en) | 2013-04-15 | 2014-10-23 | Corning Incorporated | Low diameter optical fiber |
US20150071595A1 (en) * | 2013-09-12 | 2015-03-12 | Corning Incorporated | Fiber coatings with low young's modulus and high tear strength |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5188864A (en) | 1988-08-15 | 1993-02-23 | Dow Corning Corporation | Adhesion promoter for UV curable siloxane compositions and compositions containing same |
US4921880A (en) | 1988-08-15 | 1990-05-01 | Dow Corning Corporation | Adhesion promoter for UV curable siloxane compositions and compositions containing same |
US5242963A (en) | 1991-04-10 | 1993-09-07 | Air Products And Chemicals, Inc. | Pressure sensitive adhesives comprising tackified aqueous vinyl acetate/ethylene/acrylate copolymer dispersions |
US6563993B1 (en) * | 1998-08-10 | 2003-05-13 | 3M Innovative Properties Company | Light fiber and a method for producing the same |
JP2000304987A (ja) * | 1999-04-21 | 2000-11-02 | Shin Etsu Chem Co Ltd | 光ファイバ及びその製造方法 |
JP3891247B2 (ja) * | 1999-09-27 | 2007-03-14 | 信越化学工業株式会社 | 放射線硬化型光ファイバー被覆用樹脂組成物及び光ファイバー |
JP2009024104A (ja) * | 2007-07-20 | 2009-02-05 | Nisshin Steel Co Ltd | (メタ)アクリル塗料およびこれを用いた制振材料 |
US8658163B2 (en) * | 2008-03-13 | 2014-02-25 | Curemark Llc | Compositions and use thereof for treating symptoms of preeclampsia |
KR100988526B1 (ko) | 2008-07-15 | 2010-10-18 | 김진열 | 풀림방지구가 구비된 체결수단 |
JP5724340B2 (ja) * | 2010-12-06 | 2015-05-27 | 株式会社デンソー | 光硬化性防滴材 |
CN102933629B (zh) * | 2011-01-13 | 2014-09-10 | Dic株式会社 | 自由基固化性热熔性聚氨酯树脂组合物、以及光学用成形体 |
US9708491B2 (en) * | 2014-06-04 | 2017-07-18 | Corning Incorporated | Optical fiber coating and composition |
-
2015
- 2015-05-14 US US14/711,909 patent/US9708491B2/en active Active
- 2015-06-04 WO PCT/US2015/034094 patent/WO2015187899A1/en active Application Filing
- 2015-06-04 CN CN201580040371.5A patent/CN106795389B/zh active Active
- 2015-06-04 JP JP2016571046A patent/JP6803752B2/ja active Active
- 2015-06-04 EP EP15733567.0A patent/EP3152262B1/en active Active
-
2017
- 2017-05-01 US US15/582,966 patent/US10030164B2/en active Active
-
2018
- 2018-07-23 US US16/042,051 patent/US10377915B2/en active Active
-
2020
- 2020-08-03 JP JP2020131647A patent/JP2020200467A/ja not_active Abandoned
Patent Citations (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4474830A (en) | 1982-12-29 | 1984-10-02 | At&T Bell Laboratories | Multiple coating of fibers |
US4581165A (en) | 1984-06-14 | 1986-04-08 | Eli Lilly And Company | Anti-diabetic compounds |
US20030044140A1 (en) * | 1999-12-30 | 2003-03-06 | Fewkes Edward J. | Composition containing tackifier and method of modifying time-sensitive rheological properties of optical fiber coating |
US6563996B1 (en) * | 1999-12-30 | 2003-05-13 | Corning Incorporated | Optical fibers prepared with a primary coating composition including a monomer with a pendant hydroxyl functional group |
WO2005017053A1 (en) | 2003-08-13 | 2005-02-24 | Luvantix Co., Ltd. | Photocurable and antistatic resin composition for coating optical fiber |
US20080161443A1 (en) * | 2003-08-13 | 2008-07-03 | Dae Sung Lee | Photocurable and Antistatic Resin Composition For Coating Optical Fiber |
US20050148738A1 (en) * | 2003-11-25 | 2005-07-07 | Leon Joseph A. | Caprolactone-grafted phenoxy resin oligomer and formulations containing it |
US7010206B1 (en) | 2004-09-08 | 2006-03-07 | Corning Incorporated | Coated optical fiber and optical fiber coating system including a fast-gelling primary coating |
US20080125546A1 (en) * | 2004-09-24 | 2008-05-29 | Hiroshi Yamaguchi | Curable Liquid Resin Optical Fiber Up Jacket Composition |
US8093322B2 (en) * | 2005-10-27 | 2012-01-10 | Corning Incorporated | Non-reactive additives for fiber coatings |
WO2008076299A1 (en) | 2006-12-14 | 2008-06-26 | Dsm Ip Assets B.V. | D1363 bt radiation curable primary coatings on optical fiber |
WO2010008174A2 (en) * | 2008-07-16 | 2010-01-21 | Sscp Co., Ltd. | Photocurable coating composition which provides a coating layer having improved hot water resistance |
EP2322576A2 (en) | 2008-08-26 | 2011-05-18 | SSCP Co., Ltd. | Photopolymerized resin composition and optical fiber manufactured with same |
US20120196122A1 (en) * | 2009-12-17 | 2012-08-02 | Timothy Bishop | Led curing of radiation curable optical fiber coating compositions |
US20110217011A1 (en) * | 2010-03-02 | 2011-09-08 | Kevin Wallace Bennett | High numerical aperture multimode optical fiber |
WO2014081004A1 (ja) | 2012-11-22 | 2014-05-30 | 日本合成化学工業株式会社 | 活性エネルギー線硬化性樹脂組成物、コーティング剤組成物、及び積層体 |
WO2014172143A1 (en) | 2013-04-15 | 2014-10-23 | Corning Incorporated | Low diameter optical fiber |
US20150071595A1 (en) * | 2013-09-12 | 2015-03-12 | Corning Incorporated | Fiber coatings with low young's modulus and high tear strength |
Non-Patent Citations (1)
Title |
---|
International Search Report, issued in connection with corresponding PCT application No. PCT/US2015/034094, Sep. 8, 2015. |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20170233600A1 (en) * | 2014-06-04 | 2017-08-17 | Corning Incorporated | Optical fiber coating and composition |
JP2017525782A (ja) * | 2014-06-04 | 2017-09-07 | コーニング インコーポレイテッド | 光ファイバ被覆及び組成 |
US10030164B2 (en) * | 2014-06-04 | 2018-07-24 | Corning Incorporated | Optical fiber coating and composition |
US10377915B2 (en) | 2014-06-04 | 2019-08-13 | Corning Incorporated | Optical fiber coating and composition |
Also Published As
Publication number | Publication date |
---|---|
JP2017525782A (ja) | 2017-09-07 |
US20180327625A1 (en) | 2018-11-15 |
EP3152262A1 (en) | 2017-04-12 |
JP6803752B2 (ja) | 2020-12-23 |
EP3152262B1 (en) | 2019-04-10 |
US10030164B2 (en) | 2018-07-24 |
CN106795389A (zh) | 2017-05-31 |
JP2020200467A (ja) | 2020-12-17 |
CN106795389B (zh) | 2020-03-17 |
US20150353757A1 (en) | 2015-12-10 |
US20170233600A1 (en) | 2017-08-17 |
US10377915B2 (en) | 2019-08-13 |
WO2015187899A1 (en) | 2015-12-10 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US10377915B2 (en) | Optical fiber coating and composition | |
JP4931582B2 (ja) | 被覆光ファイバおよび光ファイバを被覆するのに適した硬化性組成物 | |
US9678247B2 (en) | Primary optical fiber coating composition containing non-radiation curable component | |
US9128245B2 (en) | Low cost, fast curing optical fiber coatings | |
US10640654B2 (en) | Optical fiber coating and composition with UV-absorbing additive | |
JP2006528374A (ja) | 光ファイバ被覆系および被覆光ファイバ | |
US20160177092A1 (en) | Optical fiber coating composition with non-reactive reinforcing agent | |
CN112074493A (zh) | 具有低拔出力的光纤涂层 | |
US11319456B2 (en) | Fiber coating compositions with acylgermane photoinitiators | |
US11028214B2 (en) | Synthesis of oligomer for optical fiber coating | |
US7010205B2 (en) | Coated optical fiber and optical fiber coating system including a hydrophilic primary coating | |
US11555133B2 (en) | Fiber coating compositions with high cure speed | |
WO2009082221A1 (en) | Radiation-curable resin composition containing dipropyl or dibutyl amine |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: CORNING INCORPORATED, NEW YORK Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:BOTELHO, JOHN WILLIAM;TANDON, RUCHI;REEL/FRAME:035637/0060 Effective date: 20150513 |
|
STCF | Information on status: patent grant |
Free format text: PATENTED CASE |
|
MAFP | Maintenance fee payment |
Free format text: PAYMENT OF MAINTENANCE FEE, 4TH YEAR, LARGE ENTITY (ORIGINAL EVENT CODE: M1551); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY Year of fee payment: 4 |
|
CC | Certificate of correction |